CN101328414A - Oiling solvent oil of waste high polymer, novel process and apparatus of lubricating material - Google Patents

Abstract

The invention relates to a novel process and equipment for oiling solvent naphtha and a lubricating material from a waste high molecular substance. The process is characterized in that: 1. a substance which is not suitable for regeneration because of aging and dirtiness can be continuously fed by a vertical pyrolysis coking device which repeatedly and mechanically uses heavy oil as a medium by adopting the process for pyrogenation; energy consumption of the process is lower than that of the other processes; the production capacity of a single tank volume of the process is a plurality of times higher than that of the other processes; oil produced by the process can be processed into various machine oil through polymerization (and condensation), and reacted saturated hydrocarbon which is not polymerized is produced into the solvent naphtha via purification; 2. compared with the other processes, the process for carrying out thermal cracking on scrap rubber (and scrap plastics) which can not be regenerated through hot steam has the advantages of high thermal efficiency, low energy consumption, low manpower cost and low investment, and is capable of carrying out mass unit operation; and 3. other processes do not treat pyrolysis gas of the scrap rubber and the scrap plastics, which is over 15 percent, so production for the scrap rubber and the scrap plastics is forbidden, and market commodities do not occur simultaneously, but the process carries out tower absorption, chemical purification treatment on waste gas and controls the waste gas, and can be industrialized in a large scale. The market commodities can be various kinds of solvent naphtha, machine oils, grease lubricants and purified fuel gas.

Description

The oiling solvent oil of waste high polymer thing and lubricant novel process and equipment

1, project of the present invention " the waste high polymer thing " that refer to

(1) be unfavorable for the regenerated plastic waste promptly since aging, inclusion can't the segregator, too dirty, dust is difficult for the eliminator.

(2) can't be processed into the waste rubber article of " regenerated rubber ", aging article and the waste rubber thing that has are because its structure etc. make the too high and nullifier of regeneration tooling cost.

2, the account of the history of above-mentioned two big class polymeric scrap materials and be reproduced the present situation of utilization is described below:

(1) thermoplastic plastic goods, various in style, can use modern " plastic breaker ", become " pellet " after the fragmentation and be processed into raw product again for each plastic molding and processing plant, for the plastic waste that can not be processed into pellet, can not find again at present and utilize approach can only regard refuse treatment, can be used for " thermo-cracking " promptly so-called " oiling " handles, last decade comes, had repeatedly and similarly it is reported, report on the TV " plastic waste refining vapour, coal, diesel oil ... " etc. was also arranged, but do not see the appearance that its commodity are arranged on the market so far.Generate electricity when incineration firing as for being used for, that is the way of having no idea, and the deflated processing cost after its burning is high to being worth disproportionate with its heat that obtains.

(2) waste rubber: industrial as you know have a large amount of " regenerated rubber " to produce, not following ten million ton of its quantity in the whole world, and technology is very ripe, same is that many waste rubber things are arranged, because quality factor, textural factor and the person of should not being processed into the reclaimed rubber, and the too high person of tooling cost, moreover the reclaimed rubber market capacity also is limited.

The U.S. is used for landfill (staying disaster to the descendant) in early days, and heavy sea (staying disaster to the world) is used in reclaimed rubber and the tyre retreading in a large number, only is 30% of its raw material also, thus accumulate every year in 1,000,000 tons, Nian Funian accumulates.Data the Government is arranged in the method for disposal that certain place, state sets up a burning damaged tire generating, specialize in a railway, by government subsidy.And paying the damaged tire handling when new tyre is sold, is the way of having no idea.

Pyrolytic process is handled in history common several characteristics, fails effectively to overcome.

(1) all be that small-sized (difficulty has super 1M ³) outer hot iron bucket retort, the exchanging heat of being heated diffusion and can not be too big, horizontal in the majority, with tubulation or coil condenser, no gas-liquid separation device, no collection and confinement of gases body device, splitting gas is not handled.

(2) fire coal whenever makes one ton of destructive distillation (oily matter) liquid, consumption coal 2-3 ton, artificial 9-12 person-time of oil/consumption per ton.

(3) the every M of retort ³Can hold plastics (relic) 100-200 kilogram, the waste rubber bulk can reach the 200-300 kilogram, feeded 1-2 consuming time hour, collect distillate from heating and stop 12-16 consuming time hour, through naturally cooling more than 8 hours, go out waste material (plastics are very bothersome), can operate a batch (have and in the plastics dry distiller, be added with stirring) in 24 hours as last logical steam person.

Can receive plastic hot cracked oil 50-60%, every jar of 100-120 kilogram.

Can receive rubber oil 45% because the useful volume utilization ratio is very low, receive 140 kilograms for every jar.

Report in (4) 1977 years Reference News that Britain company makes " rubber oil " and is used as the fuel use, but do not see marketing is arranged, I " declared invention " (do to be copied in the Cultural Revolution and do not had data) in 1970 to the Sichuan Province State Scientific and Technological Commission, be not patent at that time, to report the forwarding Municipal Commission of Science and Technology by provincial scientific and technological commission after half a year, change city chemical industry office, after Shi always signs suggestion, hand over the State Scientific and Technological Commission to change " Chongqing City's waste product company " and handle (always my exclusion), ten thousand longevity bridge is built " rubber oil factory " in the north of the Changjiang River, Chongqing, and by National Supply and Marketing Cooperative General Agency in Shanghai, collect domestic waste product industry personage, held " meeting of rubber oil tech outpost display ", so that national salvage station is all doing " rubber oil ", but all rests on the empyreumatic oil stage in 1 year thereafter, " heats up in a steamer once " at most to remain " the rubber oil " that can not find any use again, China did not just have rubber oil heat thereafter, so far do not see report and obtain what progress, have the people in refining rubber oil " blending is at diesel oil ", to use yet among the people, because:

(5) " splitting gas " is that a kind of cacosmia is unpleasant, and virulent material, waste rubber splitting gas especially, show to around " fallen leaves " scene of plant fairly obvious.

Aerogenesis is many during two big class goods and materials destructive distillation, from material balance all between 15-25%, this is to affect one of Several Factors that distillation process can not get developing, and be a most important factor, if do not solve is at all can't practical application, does not just say more what use " empyreumatic oil " has not sent.

4, the Processes and apparatus declared of the present invention is as follows:

The destructive distillation of plastic waste still formula: adopt upright worker, reason is that trunk is subjected to gesture even, and it is horizontal to be subjected to the gesture area to reach volumetrical effective rate of utilization serious offense greatly, and the stove construction funds invested is low, vertical shaft type furnace thermal efficiency height, and good heat preservation performance, effectively stirring is easy to install and operation.The general disposable charging of horizontal chamber oven, the volume filling rate is low, every M ³Dress 100-200 kilogram, fuel-displaced have only the 100-140 kilogram.The modern vertical retort that adopts, black furnace is dosed to the charging opening bottom, set up the propulsive feeder of horizontal spiral at the shoulder place, in the operation in still furnace temperature reached 250 ℃ of cats head and oil vapour occurred through heat exchanger, stability of flows such as condenser are fuel-displaced, at the bottom of the tower during greater than 200 ℃, the portion that opens replenishes reinforced (collapsing in the still) feeder trunk by tower bottom reboiler (by the flue gases of furnace heating), through new reinforced being softened of heat exchange, reinforced screw rod is not less than 15 screw pitch, need not compression ratio, and is equidistant, feed end strengthens the degree of depth, increase the charging space, screw rod does not hold in still its place's trunk will grow 150mm, has the airtight effect of closing as remaining portion, feeding quantity keeps 2 times of its oily discharge, turn fast 20-50 rev/min by the variable-speed motor control, reinforced trunk internal diameter Φ 100-150mm, every M ³The volume retort can reach 500 kilograms by loading packet, collects empyreumatic oil more than 300 kilograms, raises the efficiency to be more than 2 times of old-fashioned method, and the mid-mink cell focus of every still (olein heats up in a steamer stillage residue oil or collects used oil) 30-50 kilogram is equivalent to the medium heating as end oil.

(2) progress in epoch, the development of current material industry, the stainless material under 1000 ℃ of service temperatures is applied in superheated vapo(u)r and the heat exchanger, and inaccessible technology of many past is implemented again

With the under agitation logical superheated vapo(u)r more than 600 ℃ of horizontal retort, and ceaselessly continuous supplementation is reinforced, enters pyrolytic process, essentially no backflow.1M ³Still, its tower are no more than the short tower of 1.2M, and overhead gas enters first step interchanger more than 300 ℃, and following current connects superheated vapo(u)r heat exchange (heat exchange progression becomes with heat interchanging area), uses the normal temperature water-cooled condenser at last.Common stainless steel heat exchanger tube Φ 〉=50mm, condenser can must be managed Φ 〉=50mm with general carbon steel is seamless, and tubulation is after gas-liquid separator.

(3) splitting gas is handled

Splitting gas is pumped to wet gasholder by jet exhauster through gas-liquid separator and is stored.

Through small-sized Roots's machine by gas holder sucking-off force feed to by bubbling with gas dispersion in hypochlorite solutions, many organic sulfur-containings wherein, muriate are combined to be fallen, a part is oily liquids, regularly separate and remove, there is sieve-tray tower on the top on the reactor, oxidation liquid repetitiousness drip washing gas, after big gas tank is detained, can compressed machine with gas compression first step 4-5kg/cm ², through separating second stage 17kg/cm ², through separating, not condensing gas enters gas holder for using.

The waste rubber splitting gas after the hypochlorite solutions processing, removes inadequately as remaining mercaptan, can remove with the tower washing of rare strong saline oxide solution separately, and temperature is no more than 30 ℃, and alkene is difficult for being reacted under this condition, is classical chemical reaction.

(4) pyrolysis oil: certainly may not produce what vapour, coal, diesel oil, no matter from which aspect, its composition, the deflated that is produced after burning is chloride, sulphur, phosphorus, nitrogen low-molecular material all are pyritous etching reagent, engine cylinder and valve all are unaffordable, more do not say other burning indexs.

Be to look for the use outlet on the lubricant with their machine directions now.

The first cover technology:

A, with cracking crude oil (outside the chuck water-cooled is arranged) in the vertical response jar, be filled to 70% volume, start stir per minute 100-300 section all can (visual response heat release and decide), the vitriol oil with 98% (d 1.84), 2% dosage under agitation drips, and temperature of reaction is no more than 40 ℃, adds to sulfuric acid, no longer rise to temperature, promptly begin to descend and then think first terminal point, drop to normal temperature (on temperature decide) 10 ℃-25 ℃ (be decided by water temperature) in oily temperature this moment, sees that obviously viscosity increases that (requirement is decided according to the polymerization situation, the rubber oil viscosity is very big, mixer motor is implemented the amperometer monitoring), determine operation, left standstill 24 hours, draw upper strata polymer oil mixing oil, through washing, alkali lye is handled, and considers the operation of sulfonation emulsion, can handle by the substep alkali salt, leave standstill clear and bright back and go down the step fractionation with thenardite dehydration (applying mechanically repeatedly).

B, dehydrate is distilled straight fire heating in vertical retort, slowly heat up, note being warming up in the still between 90 ℃-110 ℃ for the operational hazards time of the stove that overflows, promptly boil over the stage, prevent that way from being tapping valve standard-sized sheet at the bottom of the tower, close the excessive valve of side, spillage oil can be delivered to outside 30 meters of stills in the receiver, transfer lime is not less than φ 100mm, in case ignite, the still temperature can only slowly heat up during-140 ℃ this through 110 ℃, could strengthen the furnace temperature lift velocity after conscientiously measuring water oil discharge situation.

Collect following boiling range product:

---still temperature---110 ℃ (cat head comprise contain water section)

Export by cat head for 110 ℃-150 ℃

150℃-200℃

200℃-250℃

250-300℃

Residual oil is for greater than 300 ℃ of persons (another kind of situation can adopt destructive distillation till do---coking is handled, and coking oil is sneaked into processing repeatedly in the crude oil) in the still

C, Residual oil concentrate in another still, during heated oil temperature to 300 ℃, feed 400 ℃ of beginnings of superheated vapo(u)r oil and progressively are warming up to 500 ℃ of superheated vapo(u)rs, and progressively strengthen straight sky according to quantity of distillate, collect 2-3 fraction, make the base oil of several machinery oil.

The second cover technology (being suitable for the rubber cracked oil most):

The full fraction of distillation is till the coking in A, the vertical retort, with the full fraction of gained in polymeric kettle with 1.84 sulphuric acid catalysis polymerizations, according to iodine number whether after separation again with aluminum chloride carry out polymerization through washing, purifying, leave standstill.

B, distillation intercepting in horizontal retort

---110 ℃ of fractions

110℃-140℃

140℃-200℃

200℃-250℃

250 ℃-300 ℃ (superheated vapo(u)r that adds vacuum and 300 ℃) gas are carried remaining residue lubricating base oils and are done

C, produce high dropping point grease, can under 150 ℃ of temperature, work with strontium stearate and other viscosifying agent.

The 3rd cover technology: the simplest processing, but economic profit is maximum

With cracked oil (rubber oil preferably or the two hybrid process) rectifying intercepting, strengthen and reflux, accurately to collect as fraction, the intersection fraction must not be above 10 ℃

---110 ℃ of first fraction

110 ℃ of-150 ℃ of second fractions

150 ℃ of-200 ℃ of the 3rd fractions

200 ℃ of-250 ℃ of the 4th fractions

250 ℃-excess oil

5, produce market application (the low molecule oils of the unreacted after manager's aggregation processing is that stable hydrocarbon is main, stable in properties, and response capacity is low, toxicity obviously descends)

(1) minimum fraction is promptly---110 ℃, can make lacquer solvent additive (limitting first and second cover technology)

In (2) 110 ℃-150 ℃, rubber solvent (especially rubber cracked oil)

(3) 150 ℃-200 ℃, make roof water-proof solvent based coating solvent.

(4) 200 ℃-250 ℃, do shale brick brickmaking and cut the rudimentary brickmaking special lube of bad oil (can increase used oil and regulate viscosity and cunning property).

(5)＞250 ℃ residual oil, Stockholm tar substitute during as rubber refining, compare with Stockholm tar, it can have the effect of enhancing tensile strength and the tenderizer coal tar and the Stockholm tar substitute of reclaimed rubber, its enhancing reason is because of reactive higher in the oil molecule structure wherein, can play addition reaction with desulfurization (obtaining plasticity-) high-temperature condition rubber hydrocarbon, form due to the new macromolecular material of part.

Vacuum fraction in (6) the first cover technologies, can be deployed into the lubricating oil of " piece " in the mechanical workout, underload, several machinery oil that middle and slow speed of revolution is used, it can play and replace the partly machinery oil and the lubricating oil of petroleum product, just can lack the relative petroleum crude oil of import if we can produce 3,000,000 tons every year, these rubbish have just found its proper value.

(7) machinery that is chopped into fritter of waste rubber, it is the manufacturing thing that I use through practice, it is carpenter's disc saw, its sawtooth is all ground off with emery wheel, and wear into blade, big block rubber is cut into fritter easily as cutting bean curd under thin water column, is beneficial to the dress still, improve space availability ratio, very Guan Jian part in the still.

(8) waste rubber can be by 500 ℃-700 ℃ superheated vapo(u)r, in vertical retort (under the straight fire heating in outside), carry out steam cracking operation, as described above, its effect is decided by the heat exchange recovery, for the first time steam returns at superheated vapo(u)r thereafter and patrols middle use, use entirely for the second time, for the third time ... the overheated original steam that provides is provided steam.

(9) waste rubber destructive distillation residue, in superheater, burn, flue is by a diffuser casing, through a plurality of dividing plates, all dust settlings, its zinc oxide is in the rear portion, its product can be made the strengthening agent in grey color and the rubber size processing, be very useful, its output has account for residue heavy 30%, contain the not zinc oxide of distillation in the ash that burnt, (refuse during the oil product polymerization is told pitch shape oil after water dilutes with dilute sulphuric acid, can refine the extreme boundary lubrication material, dilute sulphuric acid can be used for) extract, produce crystalline sulfuric acid zinc.

Claims (6)

1, remodeling continuous charging and increase end oil are done the destructive distillation of thermoplastics type's macromolecular material vertical retort, produce the Processes and apparatus of oils product.

2, vertical dry distiller is to waste rubber distillation process and equipment.

3, the application of said two devices gas-liquid separator, the utilization of gas and purification process technique and equipment.

4, have the Stockholm tar substitute of strengthening the property in several specific purpose of saturated solvent and lubricating oil, lubricating grease, machinery oil substitute and rubber size processing and the reclaimed rubber processing and promptly strengthen tenderizer as glue.

5, by reclaiming zinc oxide and zinc sulfate in the scrap rubber residue in the waste rubber cracking processing.

6, waste rubber garden dish cutting machine.